Polymers derived from diamines or aminoalcohols and trialkyl or triaryl phosphites



United States Patent US. Cl. 260-775 11 Claims ABSTRACT OF THE DISCLOSURE Flame-resistant, linear, and cross-linked phosphoruscontaining polymers are prepared from the reaction of [A] an organic phosphitee.g., triethyl phosphite, triphenyl phosphite, and [B] a compound having at least one amino group-cg, ethylenediamine; 1,4-cyclohexanebis (methylamine -aminopentanol.

This application is a division of McConnell and Coover US. 'Ser. No. 587,945, filed Oct. 17, 1966, now US. Pat. No. 3,377,409, granted on Apr. 9, 1968, which is, in turn, a continuation of McConnell and Coover U.S. Ser. No. 271,884, filed Apr. 10, 1963 now abandoned.

This invention relates to new polymeric materials wherein R is selected from the group consisting of a monovalent aliphatic radical, a monovalent alicyclic radical, and a monovalent aryl radical, and wherein R is a divalent radical selected from the group consisting of:

ZO OZ Z and I \TRO NHRNH OR-I I wherein R" is selected from the group consisting of a divalent alicyclic radical, a divalent aryl radical, a divalent aliphataic radical and wherein x is selected from the group consisting of a hydrogen atom, a monovalent aliphatic radical, a monovalent alicyclic radical, and a monovalent aryl radical, wherein h is selected from the group consisting of a hydrogen atom, a chlorine atom, and a bromine atom, wherein R" is selected from the group consisting of a divalent aliphatic radical, a divalent alicyclic radical, and a divalent aryl radical, and wherein Z is selected from the group consisting of a hydrogen atom, a monovalent 3,547,893 Patented Dec. 15, 1970 alkyl radical, a monovalent alicyclic radical, and a monovalent aryl radical.

The cross-linked polymers of the invention contain the recurring group represented by the formula:

RPR

wherein R' is as defined above and Y is a divalent substance selected from the group represented by the formulas:

wherein R" and Z are as defined above.

Heretofore, it was thought that heating a mixture of a phosphite, for example, a trialkyl phosphite, and a diamine or aminoalcohol would result in alkylation of the amine rather than formation of a linear polymer. Consequently, the polymers of the present invention which are of high molecular weight and highly flame resistant were not considered possible.

A principal object of the invention, therefore, is to provide new phosphorus-containing polymers useful in their linear states and capable of cross-linking to dimensionally stable, insoluble products formable into fibers, sheets, and films. Further objects shall become apparent from the following description and claims.

The linear polymers having the above general formula:

-Rl|?-R' are obtained according to the following reactions:

wherein R, R, R", and Z are as defined aboverReacti ons (C) and (D) are carried out using the phosphorus-containing products of reactions (A) and (B) having termin31 I groups, respectively.

3 Also according to the invention, the phosphorus-containing reaction products obtained by using a mixture of and containing both amino and alcohol end groups may be reacted with diisocyanates to give products having recurring structural units such as (E) below:

wherein R, R, R", and Z areas defined above.

In preparing the cross-linked polymers having recurring groups of the formula:

R-PR- wherein R' and Y are as defined above, the reaction temperature was carefull controlled below about 200 C. iintil the third -OR group was removed from the phosphorus and cross-linking by the amine or amino alcohol occurred.

The products of this invention are flame resistant and may be advantageously employed for the color stabilization. of other polymeric materials such as polyesters, polyamides, or polyolefins. The high molecular weight polymers may be cast into flame-resistant films or molded into shaped articles.

Suitable phosphites which may be used in this invention include the trimethyl, triethyl. tributyl, triisobutyl, trioctyl, tris(2-ethylhexyl), trilauryl, triphenyl, tritolyl, and tricyclohexyl phosphites. It is also possible to use mixed phosphites such as the methyldiethyl, ethyldibutyl, ethyldiphenyl, 2 ethylhexyldiphenyl, and diphenyltolyl phosphites.

Suitable diamines which may be used in this invention include aliphatic ethylenediamine; 1,4-butanediamine; 1,6 hexanediamine; 1,10-decanediamine; and l,l2-dodecanediamine. Also, alicyclic diamines such as 1,4-cyclohexanediarnine; 1,3-cyclohexanediamine; 1,4-cyclohexanebis methylamine) 1,3-cyclohexanebis (methylamine) 1,4-cyclooctanediamine; 1,5-cyclooctanediamine; 1,4-cyclododecanediamine; 1,5-cyclododecanediamine; 2,2,4,4- tetramethyl-l,3-cyclobutanediamine; and piperazine may be used. Useful aromatic diamines include p-phenylenediamine; 4,4 isopropylidenedianiline; durenediamine; 4,4 methylenedianiline; 4,4'-methylenebis(3-chloroaniline); 4,4-methylenebis( 3-bromoaniline) 4,4-methylene bis(2,'5 dichloroaniline); 4,4 methylenebis(2,5-dibromoaniline); and related compounds. Substituted diamines such as N,N'-dimethyl-1,6-hexanediamine; N,N-dicyclohexyl 1,6-hexanediamine; and N,N-diphenyl-1,6-hexanediamine are also operable. Suitable amino alcohols include those having the general structure in which Z is H, alkyl, cycloalkyl, or aryl, and R is a divalent hydrocarbon group. Examples of such aminoalcohols include 2-aminoethanol; 3-aminopropanol; 4- aminobutanol; 4-aminopentanol; S-aminopentanol; 3- amino 2,2 dimethyl-l-propanol; 6-aminohexanol; 8- aminooctanol; 4-amino-1-cyclohexanol; 4-aminomethylcyclohexanemethanol; N-ethylaminoethanol; S-(ethylamino) 2,2 dimethyl-l-propanol; p-aminophenol; N- phenylaminoethanol; and 3 amino-2,2,4,4 tetramethyl cyclobutanol.

In order to obtain high molecular weight products, it is desirable to use approximately equimolar amounts of the phosphite and the diamine or the aminoalcohol; however, it is sometimes desirable to use an excess of the diamine or amino-alcohol so that a product containing amino or hydroxy end groups may be obtained. Such products, as mentioned above, may be subsequently reacted with diisocyanates to produce high melting poly ureas or polyurethanes. It is sometimes desirable to use a mixture of two or more diamines to impart certain specific properties to the phosphorus-containing polymers.

In general, the condensation of the diamine with the phosphite is conducted in the absence of a solvent. Inert solvents may be used, however, if desired. The operable temperature range of this reaction is about 25 C. to about 300 C. In general, the condensations are initiated at room temperature and completed at a somewhat higher temperature, for example, final temperatures of approximately 250 C. are especially suitable. Catalysts are not required for the reaction. It is advantageous to use decreased pressure toward the end of the reaction in order to remove the liberated alcohol or phenol. The end products are either extremely viscous liquids or White solid products.

If a product containing amino or both amino and alcohol end groups is reacted with a diisocyanate, it is advantageous to use an inert solvent such as the hydrocarbons, ethers, esters, and ketones, since the reactions are extremely exothermic. In this final condensation, it is advantageous to have equivalent amounts of the diisocyanate and the intermediate organophosphorous material in order to obtain high molecular weight polymers.

The following examples will further serve to illustrate the invention.

EXAMPLE 1 Polymer derived from triethyl phosphite and 1,6-hexanediamine Anhydrous 1,6-hexanediamine 0.2 mole) was mixed with triethyl phosphite (0.2 mole) and heated in the presence of nitrogen. As the reaction temperature reached approximately C., ethyl alcohol was liberated. The evolved ethyl alcohol was distilled from the reaction mixture as formed. The reaction was conducted until the theoretical amount of ethyl alcohol had been liberated (0.4 mole). The maximum reaction temperature used was 250 C. and vacuum was employed during the later stages of the reaction to remove the last traces of ethyl alcohol. This polymeric material was an extremely viscous, colorless oil at 250 C. and a White solid at 25 C. An infrared spectrum of the product indicates bands for --NH groups and POC H groups, and this spectrum is compatible with the recurring structure:

Similar polymeric materials were obtained when triethyl phosphite was treated with 1,4-cyclohexanebis-(methylamine); p-phenylenediamine; and N,N'-dimethyl-l,6- hexanediamine. Similar results were also obtained when trimethyl phosphite, trilauryl phosphite, triphenyl phosphite, and ethyl diphenyl phosphite were used instead of triethyl phosphite.

EXAMPLE 2 Polyurea from the reaction product of triethyl phosphite and 1,6-hexanediamine Anhydrous 1,6-hexanediamine (0.4 mole) and triethyl phosphite (0.38 mole) were reacted according to the procedure of Example 1 to produce a low molecular weight product containing amino end groups. About one gram of this product was treated with one gram of 2,4-tolylene diisocyanate. An extremely vigorous reaction took place and a white solid polymer was obtained immediately. This polymer was insoluble in acetone and benzene but it was partially soluble in hot dimethyl formamide. Films cast from this hot solution were transparent, tough, and had excellent flame resistance. The polymer may be represented by the recurring structural unit:

-P-NH(OHz)aNHCONH CzHs Similar polymers were obtained using 4,4'-diphenylmethane diisocyanate and 1,4-cyclohexylenedimethylene isocyanate instead of the 2,4-tolyene diisocyanate.

7 EXAMPLE 3 Polymer derived from triethyl phosphite and 4-aminomethylcyclohexanemethanol Triethyl phosphite (0.2 mole) and 4-aminomethylcyclohexanemethanol (0.2 mole) were reacted according to the procedure described in Example 1 to produce a polymeric product which may be represented by the recurring structural unit:

Similar results were obtained using other trialkyl or triaryl phosphites and other aminoalcohols.

EXAMPLE 4 Polyurethane from the reaction product of triethyl phosphite and S-aminopentanol Triethyl phosphite (0.2 mole) and S-aminopentanol (0.23 mole) were reacted according to the procedure of Example 1 to produce a low molecular weight prepolymer. When this material was treated with hexamethylene diisocyanate, a high molecular weight polymer was formed which consisted essentially of the recurring structural unit:

Similar results were obtained using 4,4'-dipheny1- methane diisocyanate; 2,4-tolylene diisocyanate; or 1,4- cyclohexylenedimethylene isocyanate instead of the hexamethylene diisocyanate.

EXAMPLE 5 Polymers derived from triphenyl phosphite and 1,4-cyclohexanebis(methylamine) Triphenyl phosphite (0.1 mole) and 1,4-cyclohexanebis(methylamine) (0.1 mole) were mixed and heated to 180 C. with stirring for 1.5 hours in the presence of dry nitrogen. The temperature of the reaction mixture was lowered to 120 C. and vacuum was gradually applied to remove the liberated phenol. The temperature was gradually raised to about 180 C. at a pressure of about one mm. of Hg and maintained under these conditions until the theoretical amount of phenol (0.2 mole) had been removed. The viscosity of the melt increased as the reaction proceeded and the final melt is an extremely viscous, light amber oil at 200 C. The molecular weight of this product is greater than 1,000 and its structure may be represented by the recurring structural unit:

Similar results were obtained using butyl diphenyl phosphite or dibutyl phenyl phosphite instead of the triphenyl phosphite except that a mixture of butyl alcohol and phenol was removed during the course of the reaction rather than phenol alone. The reaction was repeated except that 0.1 gram of sodium methoxide was added to the reaction mixture. The sodium methoxide acted as a catalyst and accelerated the removal of the phenol. Other compounds found to have a catalytic effect included sodium phenoxide, sodium amide, lithium phenoxide, zinc acetate, and diphenyl hydrogen phosphite.

6 EXAMPLE6 Cross-linked polymer derived from triphenyl phosphite and N,N'-dimethyl-1,4-cyclohexanebis(methylamine) Triphenyl phosphite (0.2 mole) and N,N'-dimethyl-l,4- cyclohexanebis(methylamine) (0.3 mole) were reacted according to the procedure of Example 5 except that the maximum reaction temperature was 200 C. A total of 0.51 mole of phenol was removed during the reaction and this cross-linked product may be represented by the recurring structural unit:

IIICHa H CHzN OH H (III-I2 IITCHs Treatment of this polymer with hexamethylene diisocyanate yielded a highly cross-linked material which is insoluble and infusible. The reaction was repeated using 0.1 gram of sodium methoxide as a catalyst to facilitate the removal of the phenol. Similar results were obtained using sodium diphenyl phosphite and also diphenyl hydrogen phosphite as catalysts. Similar results were also obtained when piperazine was used instead of the N,N- dimethyl-1,4-cyclohexanebis (methylamine) EXAMPLE 7 Polymer derived from tricyclohexyl phosphite and 2,2,4,4-tetramethylcyclobutanediamine Tricyclohexyl phosphite (0.2 mole) and 2,2,4,4-tetramethylcyclobutanediamine (0.2 mole) were reacted according to the procedure of Example 5 to liberate cyclohexanol and produce a polymeric material which may be represented by the recurring structural unit:

Similar results were obtained using dicyclohexyl ethyl phosphite, cyclohexyl diphenyl phosphite, or butyl cyclohexyl tolyl phosphite instead of the tricyclohexyl phosphite.

EXAMPLE 8 Cross-linked polymer derived from tritolyl phosphite and 3-(methylamino)-2,2-dimethyl-1-propanol Tritolyl phosphite (0.2 mole) and 3-(methylamino-2,2 dimethyl-l-propanol) (0.3 mole) were reacted according to the procedure of Example 5. A total of 0.52 mole of cresol was removed durin the reaction and the crosslinked, light amber product may be represented by the recurring structural unit:

t -1lNCHzC(OH Cl-I2O- CHE-III CH2 (]3(CHa)2 8 Treatment of this polymer with tolylene diisocyanate Z Z O Z Z gave a highly cross-llnked material WhlCh is insoluble and I H I II m II I H I infusiblel -N-R -CNHR NI-I-C-N-R N- EXAMPLE 9 and Polymer derived from triphenyl phosphite and 4,4'- f f methylenebis(3-chloroaniline) NR"-OCNHR-NH)ORN Triphenyl phosphite (0.1 mole) and 4,4'-Inethylenebiswherein R" is selected from the group consisting of an (3-chloroaniline) (0.1 mole) were reacted according to alkylene fadlcal, a cycloalkylene radical, and all afylfine the procedure of Example 5. The theoretical amount of l and wherein Z is Selected from the group Consistphenol (0.2 mole) was removed and the structure of this 10 g Of a hydrogen atom, an alkyl radical, a cycloalkyl solid polymeric product may be represented by the reradical, a an y radicalcurring structural unit: 2. A hnear polymer as defined by claim 1 and containing the recurring group I|NHCHz-NH I C H O 5 5 d1 01 OR Similar results were obtained when 4,4-rnethylenebis(3- wherein R is ethyl and is bromoaniline) or 4,4-'-methylenebis(2,5-dichloroaniline) were used instead of the 4,4'-methylenebis(3-chloro- H H O CH=I H aniline). I I II I I E A L 10 2)eN NH NHCN(CH2)0N Polymer derived P triphenyl phosphite, f pl f y 3. A linear polymer as defined by claim 1 and containhydrogen phosphite, and 4,4 -methylened1an1l1ne mg h recurring group Triphenyl phosphite (0.02 mole), diphenyl hydrogen phosphite (0.08 mole), and 4,4-methy1enedianiline (0.1 I mole) were reacted according to the procedure of Ex- 0R ample 5. The theoretical amount of phenol was obtained wherein R is ethyl and R is (0.2 mole) and the structure of the polymer obtained 4. A linear polymer as defined by claim 1 and containmay be represented by the recurring structural units: ing the recurring group -RPR H 40 wherein R is ethyl and R is and f 0 H H II I I H2)eN-C-NH-CHz-C CHz-NHCN(CH 09555 5. A linear polymer as defined by claim 1 and contain- Similar results are obtained using other molar ratios of mg the recumng group triphenyl phosphite and diphenyl hydrogen phosphite. For

example, the molar ratio of triphenyl phosphite to di- 5 phenyl hydrogen phosphite may be varied from 95/5 to I 5/95. Similarly, good results are obtained using mix- Whemm R15 ethyl and R 15 tures of trialkyl and dialkyl hydrogen phosphites such as f 0 H mixtures of triethyl phosphite and diethyl hydrogen phos- -N(CHz)50CNH(OH2)eNHii0(oH 1iI- phite, mixtures of tributyl phosphite and dibutyl hy- A linear O1 drogen phosphite or mixtures of triphenyl phosphite and ing the recurigg g f defined by damn I and contamdibutyl hydrogen phosphite. Similar results are also obtained using an aminoalcohol such as 4-aminomethylcyclohexanemethanol instead of the diamine. OR

The invention has been described in detail with particwherein R is ethyl and R is l p 11 *N (CH2)5O TC NH -CH2-NHCO(CH2)5ILI ular reference to preferred embodiments thereof but it 7 A linear 01 a s d will be understood that varlatlons and modifications can ing the recurrigg group efined by damn I and coma! be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended r RI P RI claims. I

The embodiments of the invention in which an exclu- OR sive property or privilege is claimed are defined as follows:

1. Linear polymers containing the recurring group wherein R is ethyl d R is -R'-PR'-- wherein R is selected from the group consisting of an alkyl radical, a cycloalkyl radical, and an aryl radical, I H and wherein i a divalent radical selected from the #5 N(CHZ)5O NH NHi 0-(CH -1 I- group represented by the formulas 9. Cross-linked polymers containing the recurring 11. A cross-linked polymer as defined by claim 9 and group containing the recurring group RI P RI RPR i i may. Belem wherein R is a divalent radical selected from the group wherein Y is represented by the formulas CH3 CH3 f -I I-o1-n-( :-o1no- NR-NGNHRNHCNRN and and R is I, 3

O i O 11 N-R-OCNHRNHOORN CH3 CH; O 3 0 CH3 CH3 wherein R" is selected from the group consisting of an l alkylene radical, a cycloalkylene radical, and an arylene radical, wherein Z is selected from the group consisting CH1 CH3 of a hydrogen atom, an alkyl radical, a cycloalkyl radical,

and an aryl radical, and wherein Y is a divalent radical References cued selected from the group represented by the formulas UNITED STATES PATENTS Z Z Z 3,153,0l3 10/1964 Campbell 260-77.S

l I I and DONALD E. CZAJA, Primary Examiner wherein R" and Z are as defined above.

10. A cross-linked polymer as defined by claim 9 and 40 WELSH Assistant Examiner containing the recurring group US, C], X R

i R-P-R- Fag? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3; 5 7; Dated December 5, 970

I ve q Richard L. McConnell and Harry W. Coover, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Claim 2, Column 8, the second formula. should read:

H HO 0H H I" l Signed and sealed this 20th day of April 1971.

(SEAL) Attest:

ICDZ'JARD I IJ LIETCHIEILJH. WILLIAM E. SCHUYLER, JR. Attesting Offlcer Commissioner of Patents 

